CN104039841A

CN104039841A - Catalyst component

Info

Publication number: CN104039841A
Application number: CN201280064680.2A
Authority: CN
Inventors: 乔基·基皮阿尼; 蒂莫·莱诺宁; 彼得·德尼弗; 雷约·姆拉瑞; 托米·克罗格罗斯
Original assignee: Borealis AS
Current assignee: Borealis AG; Borealis AS
Priority date: 2011-12-30
Filing date: 2012-12-19
Publication date: 2014-09-10
Anticipated expiration: 2032-12-19
Also published as: IN2014DN05988A; US20170066852A1; WO2013098139A1; EP2610273A1; EP2610273B1; JP2015503646A; JP5992534B2; CN104039841B; KR20140107637A; US20140378298A1; ES2665889T3; KR101688709B1

Abstract

The invention relates to a particulate Group 2 metal/transition metal olefin polymerisation catalyst component comprising a special 1,3-diether as internal donor, to a process for preparing same and to the use of such a catalyst component for preparing a catalyst used in the polymerisation of olefins.

Description

Catalyst component

Technical field

The present invention relates to a kind of particle olefin polymerization catalyst components that particularly comprises group II metal and for the preparation of the method for this catalyst component.The invention still further relates to the purposes of the catalyzer using in the polymerization of this catalyst component for the preparation of alkene.

Background technology

Z-N (ZN) type polyolefin catalyst is known in polymer arts, conventionally, it comprises that (a) is by periodictable (IUPAC, Nomenclature of Inorganic Chemistry, 1989) compound of transition metal of the 4th Zhi of family 6 families is, the compound of the compound of the metal of periodictable (IUPAC) the 1st Zhi of family 3 families and optional periodictable (IUPAC) 13 family and/or at least one catalyst component that inner donor compound forms.ZN catalyzer also can comprise the catalyst component that (b) is other, such as promotor and/or external donor.

The whole bag of tricks for the preparation of ZN catalyzer is well known in the art.In a currently known methods, loading type ZN catalyst system is by infiltrating catalyst component to prepare on particulate carrier materials.In WO-A-0155230, catalyst component loads on porous, inorganic or organic granular solid support material (such as silicon-dioxide).In the method for knowing at another, (magnesium compound for example, such as MgCl based on a kind of catalyst component for solid support material ₂).This class solid support material can also variety of way form.The EP-A-713886 of Japan Olefins has described: with alcohol, form MgCl ₂adducts, then by this MgCl ₂adducts emulsification and finally by the mixture quenching of generation to cause solidifying of drop.

Alternatively, the EP-A-856013 of BP discloses the formation of solid Mg base carrier, wherein by comprise Mg component be dispersed in mutually in external phase and by two-phase mixture being added liquid hydrocarbon make the Mg solidifying disperseing.

Conventionally by transistion metal compound and optional other compound treatment that are used to form active catalyst for the solid carrier particle of formation.

Therefore, externally in the situation of carrier (disclosing above the example of some outer carrier), a limiting factor (s) of the form that the form of carrier is final catalyzer.

The shortcoming that load type catalyst system runs into is that on solid support material, surface chemistry and the surface tissue of solid support material depended in the distribution of catalytic activity compound.Result is that this often can cause the uneven distribution of catalyst particles intragranular active ingredient.Due to the uneven distribution of catalyst particles intragranular avtive spot, obtained inhomogeneous catalyzer between the particle between the inhomogeneous and independent particle of granule interior, this finally causes the inhomogeneous of polymer materials.

In addition, solid support material will be stayed in final polymkeric substance as residue, and this may be harmful to some polymer application.

WO-A-0008073 and WO-A-0008074 have described the other method for the preparation of solid ZN catalyzer, have wherein formed the solution of Mg based compound and one or more other catalyst compound, and by heating systems, its reaction product have been precipitated from solution.In addition, EP-A-926165 discloses another kind of intermediate processing, wherein by MgCl ₂with the mixture of alkoxyl magnesium and Ti compound coprecipitation to produce ZN catalyzer.

According to US2005/0176900, first make magnesium compound, alcohol, ether, tensio-active agent and alkyl silicate react to obtain support of the catalyst, then make this carrier further react with titanium compound.By precipitation, obtain solid titanium catalyst component.Catalyst component comprises inner to body in addition, and this inside can be selected from multiple compounds to body.

WO03/000757 and WO03/000754 have described a kind of method for the preparation of olefin polymerization catalyst components, the method can be prepared the solid particulate of the catalyst component that comprises group II metal and transition metal, yet do not use any outer carrier material or do not use conventional intermediate processing, but using for the preparation of emulsification-curing solid catalyst particle, so-called.In this method, in the process of preparing at catalyzer, by certain method and use chemical substance original position, prepare phthalic ester type internal electron to body, make to form emulsion.The drop of the disperse phase of emulsion forms catalyst component, and curing drop produces solid particle catalyst.

WO2004/029112 discloses the further improvement of emulsification-curing of describing in WO03/000757 and WO03/000754, and therefore relate to a kind of method for the preparation of olefin polymerization catalyst components, wherein the method is characterised in that in addition, specific alkylaluminium cpd is contacted with catalyst component, activity can be increased to a certain degree under higher temperature.

Therefore,, although done a lot of developments in Ziegler-Natta catalyst field, still need method optional or improvement, that prepare the ZN catalyzer of the character with needs.

Summary of the invention

Therefore, if the method for the preparation of solid olefin polymerization catalyst components can obtain, the character (form needing and/or granularity) that the method allows to depend on granules of catalyst needs by different way (as by precipitation or emulsification/curing) form this ingredient of solid catalyst, thereby in process prepared by catalyzer, not forming the polymer property (as melt flow rate (MFR), xylene soluble part content etc.) that the material of similar gels and the catalyzer of preparation have needs, will be very favorable.In the situation that preparing propylene-ethylene random copolymer, the key feature that degree of randomness is affect polymer properties.

Another aspect of the present invention is to avoid using the material be considered to compound that may be harmful to healthy aspect and environment aspect as far as possible.A class material that is considered to compound that may be harmful is phthalate, and it is typically used as internal electron in Ziegler-natta catalyst to body.Although in final polymkeric substance, very little to the amount of these phthalate compounds of body as the inside in catalyzer, still need to find out optional compound with replace phthalate compound and still need to obtain there are generation needs the excellent activity of polymer property, the catalyzer of excellent form.

Non-phthalic ester is not originally new to the purposes of body in ZN catalyzer.Yet, should be mainly used in by catalyst component being loaded on to the catalyzer of preparing in outer carrier to body.The shortcoming of such catalyzer has more than been described.

Up to now, the highstrung characteristic because emulsion in this method for preparing catalyst forms, also cannot only form emulsion by changing to body or to body presoma.Meanwhile, affect the solubleness of Mg compound by forming Mg complex compound, the body of giving of use affects precipitation behavior significantly.

Therefore,, for two kinds of methods, depend on that selected is not apparent to condition body, that be formed for respectively the emulsion of precipitation to one skilled in the art.

Therefore, object of the present invention is for providing a kind of the have chemical constitution of needs and the catalyst component of granularity.In addition, this catalyst component has the form needing.

Therefore, another object of the present invention is to provide a kind of method for the preparation of ingredient of solid catalyst, the method allows by different way (for example precipitation or emulsification/curing) to form catalyst component, but there is common mechanism and do not need in addition to use phthalate as internal electron to body, generation has the catalyst component of the chemical constitution, form and the granularity that need, and this catalyst component is applicable to the polymkeric substance that preparation has the polymer property needing.

In addition, the object of this invention is to provide the catalyzer of the application's description for the purposes of olefinic polymerization.

Unexpectedly, these objects can be specific 1 by using, and 3-diether is realized to body as inside.

In addition, find unexpectedly, ZN catalyzer, particularly phthalic ester are catalyst based compares with other, based on 1, the catalyzer of 3-diether demonstrates the hydrogen response (hydrogen response) of improvement, and this allows to use the product of the higher MFR of hydrogen preparation that compares lower amount with the catalyzer of prior art.

Therefore, the method is compared more effective with currently known methods.

In addition, have been found that and as other benefit be, the application of the invention or prepared according to the methods of the invention catalyzer, yet, use phthalic ester type to body as inside to body, can obtain having the random copolymer of propylene of the degree of randomness lower than the degree of randomness of the polymkeric substance of preparing with the corresponding catalyzer of describing in the present invention.If need to there is the polymkeric substance of higher rigidity, need to lower degree of randomness.Degree of randomness depends on the amount of comonomer.

As an example, the multipolymer of the degree of randomness low at least 3% of the multipolymer that need to prepare with catalyzer of the present invention, degree of randomness ratio is prepared to the catalyzer of body as inside to body by use phthalic ester type under identical co-monomer content is so that polymkeric substance obtains the character of needs, as rigidity.

Degree of randomness limits as follows:

Degree of randomness=random ethylene (P-E-P-) content/total ethylene content * 100%.

Invention is described

Therefore, the invention provides a kind of as the ingredient of solid catalyst limiting in claim 1.

Therefore, the present invention also provides a kind of for the preparation of as the method for the solid olefin polymerization catalyst components limiting in claim 1.

Therefore, the invention provides a kind of ingredient of solid catalyst, this ingredient of solid catalyst has:

A) within the scope of 1.0 % by weight to 10.0 % by weight, preferably within the scope of 1.5 % by weight to 8.5 % by weight, the more preferably group-4 metal within the scope of 2.0 % by weight to 7.0 % by weight, preferred Ti content (measuring by icp analysis);

B) within the scope of 5.0 % by weight to 22.0 % by weight, preferably within the scope of 6.0 % by weight to 20 % by weight, the more preferably group II metal within the scope of 6.5 % by weight to 18 % by weight, preferred Mg content (measuring by icp analysis);

C) within the scope of 0.0 to 0.8 % by weight, preferably within the scope of 0.0 to 0.5 % by weight, the more preferably Al content (measuring by icp analysis) within the scope of 0.0 to 0.4 % by weight;

D) within the scope of 2 μ m to 500 μ m, preferably within the scope of 5 μ m to 200 μ m, the more preferably mean particle size within the scope of 10 μ m to 100 μ m (by using Coulter counter LS200 to measure in normal heptane at 25 ℃);

E) be selected from 1 of formula (I) or formula (II), the inside of 3-diether or its mixture is to body:

Wherein in formula (I) and formula (II)

R ₁and R ₂identical or different, and can be straight or branched C ₁to C ₁₂alkyl, or R ₁with R ₅and/or R ₂with R ₆can form the ring with 4 to 6 C atoms,

R in formula (I) ₃and R ₄identical or different, and can be H or straight or branched C ₁to C ₁₂alkyl, or R ₃and R ₄can form together the ring with 5 to 10 C atoms, this ring can be has the aliphatics of 9 to 20 C atoms or a part for aromatic series polycyclic system,

R in formula (I) ₅and R ₆identical or different, and can be H or straight or branched C ₁to C ₁₂alkyl, or can form together the aliphatics ring with 5 to 8 C atoms,

And the R in formula (II) ₅₁, R ₆₁and R ₇identical or different, and can be H or straight or branched C ₁to C ₁₂alkyl, or R ₅₁, R ₆₁and R ₇in two or three can with C ₁to C ₃form together there are 6 to 14 C atoms, preferably aromatic ring or the member ring systems of 10 to 14 C atoms.

In addition, the invention provides a kind of method of the olefin polymerization catalyst components for the preparation of solid particulate form, the method comprises the following steps:

A) prepare the solution of at least one alkoxy compound (Ax), at least one compound that this alkoxy compound (Ax) is group II metal and the reaction product of at least one monohydroxy-alcohol (A) in liquid organic reactant medium,

B) this solution is added at least one compound of transition metal, and

C) prepare ingredient of solid catalyst particle,

Wherein at step c) arbitrary step before, by 1 of formula (I) or formula (II), 3-diether or its mixture add as inner to body:

Wherein in formula (I) and formula (II):

Preferred embodiment is described in dependent claims and following explanation.In addition, the invention provides according to the present invention obtainable catalyst component and the other catalyst component purposes in olefinic polymerization.

Below with reference to specific preferred embodiment, the present invention is described in more detail.In all embodiment, importantly, solid catalyst can be by liquid/liquid two-phase (emulsion) system-curing or intermediate processing preparation, do not need to use phthalate compound, the method causes granules of catalyst to have physical properties, the morphological feature for example particularly needing and/or the granularity of needs and the size-grade distribution of needs.

The present inventor finds unexpectedly, the form that having in embodiment needs and/or the catalyst component particle of granularity and/or size-grade distribution can be by preparing emulsification-the curing or coprecipitation mode acquisition of Z-N (ZN) type catalyzer, this catalyst component particle is suitable for olefinic polymerization (particularly propylene polymerization), but does not need to use phthalate.In addition, the chemical constitution of the chemical constitution of catalyzer of the present invention and the catalyzer of immediate prior art is different.According to print effect, use polymer beads prepared by catalyzer of the present invention also to there is the morphological properties of needs.

Catalyzer preparation of the present invention, wherein need to be such as silicon-dioxide or MgCl based on liquid/liquid two-phase system (emulsification/curing) or intermediate processing ₂independent outer carrier material to obtain solid catalyst particle.

The formation that is characterised in that especially catalyst component for the preparation of the method for solid catalyst particle comprises that using is at least one alkoxy compound (Ax) of at least one compound of group II metal and the reaction product of at least one monohydroxy-alcohol (A), and other being characterised in that in catalyzer preparation used 1 of non-phthalic ester, 3-diether itself as internal electron to body.

According to an embodiment, the reaction product of the mixture of the reaction product of at least one compound that alkoxy compound (Ax) is group II metal and monohydroxy-alcohol (A) or at least one compound of group II metal and monohydroxy-alcohol (A) and other alcohol (B), alcohol (B) also comprises oxy radical different from hydroxylic moiety, that at least one is other except hydroxylic moiety.

According to another embodiment, except being at least one alkoxy compound (Ax) of at least one compound of group II metal and the reaction product of monohydroxy-alcohol (A), also may use at least one other alkoxy compound (Bx), alkoxy compound (Bx) at least one compound of group II metal with as the reaction product of the alcohol that also comprises the oxy radicals different, that at least one is other with hydroxylic moiety except hydroxylic moiety (alcohol B) of following restriction.

Preferably, alkoxy compound is alkoxy compound (Ax), and alkoxy compound (Ax) is at least one compound of group II metal of further describing below and the reaction product of the mixture of this alcohol (A) or alcohol (A) and alcohol (B).

Alkoxy compound (Ax and Bx) can be by making the compound of this group II metal react original position to prepare with alcohol described above or alcohol mixture in method for preparing catalyst first step, or this alkoxy compound can be the reaction product of independent preparation, or it even can be the available existing compound of business and itself is for method for preparing catalyst of the present invention.

Alcohol or alcohol mixture at least one compound by group II metal and above restriction are prepared in the process of alkoxy compound (Ax or Bx), can will add in reaction mixture to body, thereby form group II metal complex compound (complex compound Ac or Bc), this group II metal complex compound is defined as at least one group II metal compound, alcohol or alcohol mixture and in this application to the complex compound of body.

If do not use anyly to form alkoxy compound (Ax) and/or (Bx) to body, will give body itself independent or add reaction product solution in the process of Kaolinite Preparation of Catalyst component.

The compound of group II metal is selected from and comprises following compound, the group preferably consisting of following compound: dialkyl group group II metal, alkyl alkoxy group II metal, alkyl group II metal halogenide and group II metal dihalide.The compound of the group II metal group that also the following compound of optional freedom forms: dialkoxy group II metal, two aryloxy group II metals, alkoxyl group group II metal halogenide, aryloxy group II metal halogenide, alkyl alkoxy group II metal, alkoxy aryl group II metal and alkyl-aryloxy group II metal.Preferably, group II metal is magnesium.

Monohydroxy-alcohol (A) is the monohydroxy-alcohol of formula ROH, and wherein R is straight or branched C ₁to C ₂₀alkyl.

Typical C ₁to C ₅monohydroxy-alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, sec.-amyl alcohol, tertiary amyl alcohol, diethyl carbinol, secondary primary isoamyl alcohol, tertiary butyl methyl alcohol.

Typical C ₆to C ₁₀monohydroxy-alcohol is hexanol, 2-ethyl-n-butyl alcohol, 4-methyl-2-amylalcohol, 1-heptanol, 2-enanthol, 4-enanthol, 2,4-dimethyl-3-amylalcohol, 1-octanol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, 1 nonyl alcohol, 5-nonyl alcohol, diisobutyl carbinol(DIBC), 1-decanol and 2,7-dimethyl-sec-n-octyl alcohol.Typical > C ₁₀monohydroxy-alcohol is n-1-hendecanol, n-DODECANOL, 1-, n-1-tridecyl alcohol, n-1-tetradecanol, n-1-pentadecylic alcohol, n-1-cetyl alcohol, n-1-heptadecanol and n-1-Stearyl alcohol.Monohydroxy-alcohol can be undersaturated, as long as it is not as catalyzer poison.

Preferred monohydroxy-alcohol is the monohydroxy-alcohol with formula ROH, and wherein R is C ₂to C ₁₆alkyl group, C most preferably ₄to C ₁₂alkyl group, particularly 2-ethyl-1-hexanol.

Alcohol (B) for also comprising the alcohol of at least one the other oxy radical different from hydroxylic moiety except hydroxylic moiety.

Typically, so other oxy radical is ether moiety.As the alcohol of above restriction (B) can be fatty compounds or aromatics, although fatty compounds is preferred.Fatty compounds can be straight chain, side chain or ring-type or its arbitrary combination, and particularly preferred alcohol is the alcohol that comprises an ether moiety.

According to the present invention, illustrative example to be used, the preferred like this alcohol that comprises ether moiety (B) is: glycol monoether, particularly C ₂to C ₄glycol monoether, such as ethylene glycol mono-ether or propylene glycol monoether, wherein ether moiety comprises 2 to 18 carbon atoms, preferred 2 to 12 carbon atoms.Preferred monoether class is C ₂to C ₄glycol monoether and its derivative.Illustrative and preferred example are: butyl glycol ether, glycol hexyl ether, ethylene glycol 2-ethyl hexyl ether, propylene glycol n-butyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol n-hexyl ether, propylene glycol 2-ethyl hexyl ether, glycol hexyl ether, 1, ammediol ether and 1,3-PD n-butyl ether are particularly preferred.

Most preferred alcohol (B) is 1,3-PD n-butyl ether.

Conventionally, different alkoxy compounds or alcohols are used with the mol ratio in 10: 1 to 1: 10 scopes, preferably this mol ratio in 8: 1 to 1: 8 scopes, more preferably in 6: 1 to 1: 6 scopes, even more preferably in 4: 1 to 1: 4 scopes and be also in an embodiment in 2: 1 to 1: 2 scopes.This be than being conditioned, depend on use to body, for example, what have short chain needs the more alcohols of long-chain to body, and vice versa.

In an embodiment, reaction for the preparation of alkoxy compound (Ax) and alkoxy compound (Bx) can preferably be carried out at the temperature within the scope of 20 ℃ to 80 ℃ in aromatic series or aromatic/aliphatic medium, and in the situation that group II metal is magnesium, the preparation of alkoxyl magnesium compound can be carried out under the temperature within the scope of 50 ℃ to 70 ℃.

As the reaction medium of solvent, can be aromatic hydrocarbon based or aromatic hydrocarbon based and mixture aliphatic hydrocarbon, the latter comprises 5 to 20 carbon atoms, preferably 5 to 16 carbon atoms, more preferably 5 to 12 carbon atoms and 5 to 9 carbon atoms most preferably.Preferably, aromatic hydrocarbons is selected from and is substituted and unsubstituted benzene, is preferably selected from alkylated benzenes, is even more preferably selected from toluene and xylene, and most preferably is toluene.

The mol ratio of this reaction medium and magnesium is preferably less than 10, for example, in 4 to 10 scopes, preferably in 5 to 9 scopes.

Alkoxy compound (Ax) and alkoxy compound (Bx) are preferably alkoxyl magnesium compound.

The group of alkoxyl magnesium compound is preferably selected from the group consisting of following compound: the complex compound of the complex compound of dialkoxy magnesium, magnesium dihalide and alcohol and magnesium dihalide and dialkoxy magnesium or its mixture.More preferably, alkoxyl magnesium compound is dialkoxy magnesium compound.

The group of alkoxyl magnesium compound is each alcohol (A), alcohol (B) or alcohol (A) and the mixture of alcohol (B) and the reaction product of magnesium compound, the group that the freely following compound of this magnesium compound choosing forms: dialkyl magnesium, alkyl alkoxy magnesium, alkyl halide magnesium and magnesium dihalide.The group that it can further select freely following compound to form: dialkoxy magnesium, two aryloxy magnesium, alkoxyl group magnesium halide, aryloxy magnesium halide, alkyl alkoxy magnesium, alkoxy aryl magnesium and alkyl-aryloxy magnesium.

Preferably, dialkoxy magnesium is for having formula R ₂the reaction product of the dialkyl magnesium of Mg and each alcohol A or alcohol B, wherein each R in two R is similar or different C ₁to C ₂₀alkyl, be preferably similar or different C ₂to C ₁₀alkyl.

Typical alkyl magnesium is ethyl-butyl magnesium, dibutylmagnesium, dipropyl magnesium, propyl group dibutyl magnesium, diamyl magnesium, butyl amyl group magnesium, butyl octyl magnesium and dioctyl magnesium.Most preferably, formula R ₂a R of Mg is that butyl group and another R are ethyl group or octyl group group, and dialkyl magnesium compound is butyl octyl magnesium or ethyl-butyl magnesium.

When using, typically alkyl alkoxy magnesium compound RMgOR is ethyl butoxy magnesium, butyl pentyloxy magnesium, octyl group butoxy magnesium and octyl group octyloxy magnesium.

The electronic donor compound capable using in the preparation process of catalyzer of the present invention is selected from 1 of formula (I) or formula (II), 3-diether

Wherein in formula (I) and formula (II)

And the R in formula (VI) ₅₁, R ₆₁and R ₇identical or different, and can be H or straight or branched C ₁to C ₁₂alkyl, or R ₅₁, R ₆₁and R ₇in two or three can with C ₁to C ₃form together there are 6 to 14 C atoms, preferably aromatic ring or the member ring systems of 10 to 14 C atoms.

In formula (I) and formula (II), R preferably ₁and R ₂identical and can be straight or branched C ₁to C ₁₀alkyl, more preferably C ₁to C ₈alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or the tertiary butyl or 2-ethylhexyl.

In formula (I), R likely in addition ₁with R ₅and/or R ₂with R ₆can form together with Sauerstoffatom there are 4 to 6 C atoms, the preferred ring of 4 to 5 carbon atoms, as tetrahydrofuran (THF) ring or amylene oxide ring.

R ₃be preferably straight or branched C ₁to C ₁₀alkyl, more preferably C ₁to C ₉alkyl, as methyl, ethyl, sec.-propyl, isobutyl-or n-nonyl.

R ₄be preferably H or straight or branched C ₁to C ₁₀alkyl, more preferably C ₁to C ₆alkyl, as methyl, sec.-propyl, normal-butyl, isobutyl-, isopentyl.

Also possibly R ₃with R ₄can form together ring, be preferably there are preferably 5 to 7 C atoms, the more preferably alicyclic ring of 5 to 6 C atoms, as pentamethylene, 2-cyclopentenes or 3-cyclopentenes, tetrahydrobenzene, 2-tetrahydrobenzene or 3-tetrahydrobenzene or 4-tetrahydrobenzene.

In addition likely, this ring is for having a part for the alicyclic or aromatic series polycyclic system (as naphthane, hydrogenation indane (hydroindane), fluorenes or indane) of 9 to 18 C atoms.

Preferably, the R in formula (I) ₅can be H or straight or branched C ₂to C ₈alkyl, more preferably can be H or C ₂to C ₆alkyl and most preferably be H.

Preferably, the R in formula (I) ₆can be H or straight or branched C ₂to C ₈alkyl, preferably H or straight chain C ₃to C ₆alkyl, as sec.-propyl or isobutyl-.

In formula (I), R likely in addition ₅with R ₆can form together the aliphatics ring with 5 to 8 C atoms, as pentamethylene, tetrahydrobenzene or suberane.

In formula (II), R ₅₁, R ₆₁and R ₇identical or different, and be preferably H or straight or branched C ₁to C ₁₀alkyl, more preferably H or straight or branched C ₁to C ₈alkyl, as methyl, sec.-propyl, normal-butyl, isobutyl-, isopentyl.

In formula (II), in addition likely, R ₅₁, R ₆₁and R ₇in two or three and C ₁to C ₃form together there are 6 to 14 C atoms, preferably aromatic nucleus or the member ring systems of 10 to 14 C atoms.Such aromatic nucleus or ring body are phenyl, naphthalene, anthracene or phenanthrene.Preferably, this ring body is naphthalene.

The compound of transition metal is preferably the compound of group-4 metal.Group-4 metal is preferably titanium, and treats that its compound of the complex compound reaction of Yu 2 families is preferably halogenide.The coordinator of titanium tetrahalide is the combination of alkoxyl group halogenated titanium and halogenating agent, and therefore, this combination can original position form titanium tetrahalide.Most preferred halogenide is muriate.

The compound of the transition metal using in the method in another embodiment of the present invention, also can comprise in this area typically organic ligand that use, that be called single-site catalysts.

Still in another embodiment of the present invention, the compound of transition metal also can be selected from the 5th family's metallic compound, the 6th family's metallic compound, Cu compound, Fe compound, Co compound, Ni compound and/or Pd compound.

In principle, this olefin polymerization catalyst components can be with all acquisitions of the various ways based on same mechanism.

The preparation of the olefin polymerization catalyst components that in one embodiment, form is solid particulate comprises the following steps:

(a1) prepare the solution (S1) of at least one alkoxy compound (Ax), the reaction product of the electron donor(ED) of at least one compound that this alkoxy compound (Ax) is group II metal and at least one monohydroxy-alcohol (A) and formula (I) or formula (II) in liquid organic reactant medium (OM1)

(b1) by this solution (S1) and at least one transistion metal compound (CT) combination,

(c1) this catalyst component that precipitation forms is solid particulate, and

(d1) reclaim the cured granulate of olefin polymerization catalyst components.

In step (a1), likely use the alkoxy compound (Ax) for the reaction product of at least one group II metal compound and monohydroxy-alcohol (A), as above restriction.

In addition likely, use the alkoxy compound (Ax) of the reaction product of the mixture that is at least one group II metal compound and alcohol (A) and alcohol (B), alcohol (B) also comprises oxy radical different from hydroxylic moiety, that at least one is other except hydroxylic moiety, as above restriction.

The third possibility is, use the mixture of alkoxy compound (Ax) and alkoxy compound (Bx), alkoxy compound (Ax) is the reaction product of at least one group II metal compound and monohydroxy-alcohol (A), alkoxy compound (Bx) is the reaction product of at least one group II metal compound and alcohol (B), alcohol (B) also comprises oxy radical different from hydroxylic moiety, that at least one is other except hydroxylic moiety, as above restriction.

Preferably, the alkoxy compound using is alkoxy compound (Ax), alkoxy compound (Ax) is the reaction product of the mixture of at least one group II metal compound and alcohol (A) and alcohol (B), alcohol (B) also comprises oxy radical different from hydroxylic moiety, that at least one is other except hydroxylic moiety, as above restriction.

Likely, the transistion metal compound in step (b1) is dissolved in liquid organic reactant medium (OM2), forms thus solution (S2).

The process of solid precipitation can be undertaken by the whole bag of tricks:

In one embodiment, in step (b1), solution (S1) is added at least one transistion metal compound (CT) at least 50 ℃, preferably in 50 ℃ to 110 ℃ temperature ranges, more preferably at 70 ℃ within the scope of 100 ℃, most preferably complete at the temperature within the scope of 85 ℃ to 95 ℃, at this temperature, at least one transistion metal compound (CT) is liquid form, and result is the precipitation of this ingredient of solid catalyst.

In this case, should be understood that especially, after solution (S1) and at least one transistion metal compound (CT) are combined, by complete reaction mixture remain at least 50 ℃, more preferably in 50 ℃ to 110 ℃ temperature ranges, more preferably at 70 ℃ within the scope of 100 ℃, most preferably at the temperature within the scope of 85 ℃ to 95 ℃, the precipitation completely of the catalyst component that the form of assurance of take is solid particulate.

In this case, likely in step (a1) or step (b1), add tensio-active agent.

The general example of tensio-active agent comprises polymeric surfactant, such as poly-(alkyl methacrylate) and poly-(alkyl acrylate) etc.Polyalkyl methacrylate is for comprising the polymkeric substance of one or more methacrylate monomer (such as at least two kinds of different methacrylate monomer, at least three kinds of different methacrylate monomer etc.).In addition, acrylic ester polymer and methacrylate polymers can comprise the monomer that is not acrylate monomer and methacrylate monomer, as long as polymeric surfactant comprises acrylate monomer and the methacrylate monomer at least about 40 % by weight.

The example of the available tensio-active agent of business comprises the Additives from RohMax, and GmbH is available, trade mark is VISCOPLEX ^(R)tensio-active agent (the particularly tensio-active agent of name of product 1-254,1-256) and from the available business's label of Noveon/Lubrizol, be CARBOPOL ^(R)and PEMULEN ^(R)tensio-active agent.

In second embodiment, at temperature by least one transistion metal compound (CT) of solution (S1) and liquid form within the scope of approximately-20 ℃ to approximately 30 ℃, mix, and subsequently by temperature is slowly elevated at least 50 ℃, preferably in the temperature range of 50 ℃ to 110 ℃, more preferably in the scope of 70 ℃ to 100 ℃, most preferably carry out precipitated solid catalyzer in the scope of 85 ℃ to 95 ℃, thereby the speed that temperature increases is in the scope of 0.1 ℃ of per minute to 30 ℃ per minute, preferably in the scope of 0.5 ℃ of per minute to 10 ℃ per minute.

In this case, be understandable that especially, in step (b1), before tensio-active agent added to solution (S1).Suitable tensio-active agent as mentioned above.

In both cases, possible but dispensable, some precipitation agents are added to system.Such precipitation agent can be realized the form of the particle forming in settling step process.In a specific method, do not use precipitation agent.According to precipitation agent of the present invention, be that promotion form is the reagent of precipitation of the catalyst component of solid particulate.As limited below in the application, as the organic liquid medium of (OM2), can promote precipitation, and therefore as and as precipitation agent.Yet final catalyzer does not comprise any this medium.

In addition, preferably, in method, do not use precipitation agent, as described above.

Preferably, the catalyst component of preparing in earlier paragraphs is the solid particulate of precipitation.

According to the present invention, the meaning of " precipitation " is, in the process of preparing, chemical reaction occurred in solution at catalyst component, causes the catalyst component of needs soluble in this solution.

Suitable alkoxy compound (Ax) and alkoxy compound (Bx) and its preparation have below been described.

Suitable electron donor(ED) and suitable transistion metal compound have below also been described.

Preferably, use TiCl ₄as transistion metal compound.

Add alkoxy compound (Ax) or alkoxy compound (Bx) (if existence) or alkoxy compound (Ax) (by mixed oxyalkyl compound (Ax) and alkoxy compound (Bx), to obtain with the mixture of alkoxy compound (Bx) electron donor(ED), this alkoxy compound (Ax) is the reaction product of at least one group II metal compound described above and monohydroxy-alcohol described above (A), this alkoxy compound (Bx) is the reaction product of at least one group II metal compound described above and alcohol described above (B)), thus serve as solvent, for the reaction medium of group II metal compound, can be the mixture of aromatic hydrocarbon based or aromatic hydrocarbon based and aliphatic hydrocarbon, the latter comprises 5 to 20 carbon atoms, preferred 5 to 16 carbon atoms, more preferably 5 to 12 carbon atoms and most preferably 5 to 9 carbon atoms.Preferably, aromatic hydrocarbons is selected from replacement and unsubstituted benzene class, is preferably selected from alkylated benzenes class, is even more preferably selected from toluene and xylene and most preferably is toluene.

If need, can to arbitrary step of step (b1), other be added to catalyst preparation process to body in step (a1).Preferably, if used, in addition to give body be also non-phthalic ester.

Also may use the mixture of two ethers described above.

Reaction medium is corresponding with the liquid organic reactant medium (OM1) of step (a1).

TiCl ₄solubilized liquid organic reactant medium (OM2) wherein can be identical or different with liquid organic reactant medium (OM1), and the latter is preferred.

Preferably, liquid organic reactant medium (OM2) is C ₅to C ₁₀hydrocarbon, more preferably C ₆to C ₁₀alkane, as heptane, octane or nonane or its mixture.

Be understandable that especially, liquid organic reactant medium (OM1) is C ₆to C ₁₀aromatic hydrocarbon, most preferably be toluene, and liquid organic reactant medium (OM2) is C ₆to C ₁₀alkane, most preferably be heptane.

In addition, should be understood that, liquid organic reactant medium (OM1) and liquid organic reactant medium (OM2) are to support the mode of precipitation immediately of solid catalyst particle to select.

When solution (S1) is added at least one transistion metal compound (CT), mixing is to be understood that.Suitable hybrid technology comprises mechanism and the ultrasonic wave of using for mixing, as is known to persons skilled in the art.

After precipitation, wash in a known manner solid catalyst particle.

Therefore, preferably, by solid catalyst particle with hydrocarbon washing at least one times to as high as 6 times, preferably at least twice, most preferably at least three times, this hydrocarbon is preferably selected from aromatic hydrocarbon based and aliphatic hydrocarbon, be preferably toluene, heptane or pentane, more preferably toluene, particularly heat (for example at 80 ℃ within the scope of 100 ℃) toluene, may comprise in this hydrocarbon more in a small amount or the TiCl of a large amount more ₄.TiCl ₄amount can be at a few volume % to being greater than 50 volume %, such as 5 volume % to 50 volume %, preferably change in the scope of 5 volume % to 15 volume %.Also possibly, with the TiCl of 100 volume % ₄carry out at least once washing.

At aromatic hydrocarbon based and/or TiCl ₄after washing, the available aliphatic hydrocarbon with 4 to 8 carbon atoms carries out the other washing of one or many.Preferably, these washings are below carried out with heptane and/or pentane.Washing available heat (for example 90 ℃) or cold (room temperature) hydro carbons or its combine to carry out.Also possibly, for all washings, identical solvent (for example toluene) carries out.

In addition,, in the process of preparing at catalyst component, can add the reductive agent of the amount of titanium that exist, that exist with oxidation state+4 in this cured granulate that has reduced olefin polymerization catalyst components.

Alkylaluminium cpd, alkyl alkoxy aluminum compound and the magnesium compound of suitable reductive agent for limiting in this specification sheets.

Suitable aluminum compound has general formula AlR _3-nx _n, wherein R represents to have 1 to 20, preferably 1 to 10 and more preferably straight or branched alkyl group or the alkoxy base of 1 to 6 carbon atom, and X represents to be selected from the residue of the group of halogen (preferably chlorine) independently, and n represents 0,1 or 2.At least one residue in R residue is necessary for alkyl group.

This compound can be used as optional compound add catalyst component synthetic in and can be in step (b1) to step (c1) however in arbitrary step or in washing step process described above, in step (d1), add before.

Preferably, in washing step, more preferably reducing compound is added in using the first washing step of hot toluene.

According to the illustrative example of alkylaluminium cpd to be used of the present invention and alkoxy aluminum compound, be:

Three-(C ₁-C ₆)-alkylaluminium cpd and (C ₁-C ₆)-alkyl aluminum chloride compound, particularly diethyl aluminum chloride;

Diethylaluminum ethoxide, ethyl diethoxy aluminium, diethyl aluminum methoxide, diethyl propoxy-aluminium, diethyl butoxy aluminium, dimethyl aluminum ethoxide, wherein diethylaluminum ethoxide is particularly preferred.

Suitable magnesium compound is that the application limits, relevant to the complex compound of group II metal magnesium compound.About the magnesium compound to be added of the method according to this invention, each open source information is incorporated to the application by reference.Especially, suitable magnesium compound is that dialkyl magnesium compound or general formula are MgR _2-nx _nalkyl halide magnesium compound, wherein each n is 0 or 1, and each R is the identical or different alkyl group with 1 to 8 carbon atom, and X is halogen, is preferably Cl.A kind of preferred magnesium compound is butyl octyl magnesium (business is available, and trade(brand)name is BOMAG), preferably, has used butyl octyl magnesium in the preparation of Mg complex compound.

The add-on of optional Al compound depends on the reducing degree of the needs of the amount of titanium that exist, that exist with oxidation state+4 in the cured granulate of olefin polymerization catalyst components.The preferred amount of Al in catalyst component depends on Al compound to a certain extent, and for example, if use Al-alkoxy compound, the amount of preferred final Al seems such as fruit is used the amount of the final Al of alkyl chlorination Al compound for example low.

Final catalyst component particle has within the scope of 0.0 to 0.8 % by weight, preferably within the scope of 0.0 to 0.5 % by weight or the Al content within the scope of 0.0 to 0.4 % by weight.

Magnesium compound to be added according to the present invention adds with corresponding amount.

Preferably, alkyl aluminum chloride compound, particularly diethyl aluminum chloride are added.

In the second way, the preparation of the catalyst component of solid particulate form comprises the following steps:

(a2) prepare the solution of at least one alkoxy compound (Ax), the reaction product of the electron donor(ED) of at least one compound that this alkoxy compound (Ax) is group II metal and at least one monohydroxy-alcohol (A) and formula (I) or formula (II) in liquid organic reactant medium

(b2) this solution of this alkoxy compound (Ax) is added at least one compound of transition metal with preparation emulsion, wherein the disperse phase of this emulsion is drop form and comprises the group II metal in this alkoxy compound (Ax) that is greater than 50 % by mole

(c2) stir this emulsion, the drop of this disperse phase is remained in this predetermined size ranges of 2 μ m to 500 μ m,

(d2) solidify this drop of disperse phase,

(e2) reclaim the cured granulate of olefin polymerization catalyst components.

In step (a2), may use the alkoxy compound (Ax) into the reaction product of at least one group II metal compound and monohydroxy-alcohol (A), as above restriction.

Also possibly, use the alkoxy compound (Ax) of the reaction product of the mixture that is at least one group II metal compound and alcohol (A) and alcohol (B), alcohol (B) also comprises oxy radical different from hydroxylic moiety, that at least one is other except hydroxylic moiety, as above restriction.

The third possibility is to use the mixture of alkoxy compound (Ax) and alkoxy compound (Bx), alkoxy compound (Ax) is the reaction product of at least one group II metal compound and monohydroxy-alcohol (A), alkoxy compound (Bx) is the reaction product of at least one group II metal compound and alcohol (B), alcohol (B) also comprises oxy radical different from hydroxylic moiety, that at least one is other except hydroxylic moiety, as above restriction.

In step (a2), solution (S1) typically is at least one alkoxy compound (Ax) and optional alkoxy compound (Bx) solution in liquid hydrocarbon reaction medium, solution (S1) can be by making the mixture of alcohol (A) or alcohol (A) and alcohol (B) react to form alkoxy compound (Ax) (as described above) with group II metal compound in liquid hydrocarbon medium and optionally mixed oxyalkyl compound (Ax) and alkoxy compound (Bx) come original position to provide, alkoxy compound (Bx) is by making alcohol (B) react to prepare in liquid hydrocarbon medium with group II metal compound.

Preferably, in step (a2), the inside limiting is above added to this solution (S1) to body.

The mixture that electron donor(ED) is added to alkoxy compound (Ax) or alkoxy compound (Bx) (if existence) or alkoxy compound (Ax) and alkoxy compound (Bx).

If need, can to arbitrary step of step (c2), other be added to catalyst preparation process to body in step (a2).Preferably, if used, in addition to give body be also non-phthalic ester.Also can use the mixture to body described above.

Then, typically the solution of step (a2) is added at least one compound of transition metal, such as titanium tetrachloride.Preferably, this be added in low temperature (such as at-10 ℃ within the scope of 40 ℃, preferably at-5 ℃ within the scope of 30 ℃, such as approximately 0 ℃ to 25 ℃ within the scope of) under carry out.

In arbitrary step of these steps, can there is the organic reaction medium or the solvent that are typically selected from aromatic hydrocarbon based and/or aliphatic hydrocarbon described above.

The emulsion of the oily disperse phase that the method according to this invention has produced (as the intermediate stage) thicker, transistion metal compound as shown above/be insoluble in toluene in the oily external phase (oil disperse phase), oil disperse phase typically has the transition metal/group II metal mol ratio in 0.1 to 10 scope, and oily external phase has the transition metal/group II metal mol ratio in 10 to 100 scopes.

Transistion metal compound is preferably group 4 metal compounds, and most preferably is TiCl ₄.Group II metal is preferably magnesium.Then optionally under the existence of emulsion stabilizer and/or the minimum agent of turbulent flow, stir this emulsion, the drop of this disperse phase is typically remained in the size ranges of 2 μ m to 500 μ m.After this particle by the disperse phase that is heating and curing for example, obtain granules of catalyst.

Therefore, this external phase and disperse phase can be distinguished by the following fact each other: if (be preferably TiCl with group 4 metal compounds ₄) contact of solution in toluene, thicker oil can not dissolve therein.The appropriate solution of setting up this standard will be the solution with the toluene mole ratio in 0.1 to 0.3 scope.This external phase and disperse phase also can be by following true differences: the most Mg (as complex compound) that are provided for react with group 4 metal compounds are present in disperse phase, as the relatively announcement by each group-4 metal/Mg mol ratio.

Therefore, in fact, almost the total overall reaction product of Mg complex compound and group-4 metal (for the presoma of final catalyst component) becomes disperse phase, and is processed as final particle form by other procedure of processing.The external phase that still includes the group-4 metal of consumption can be reprocessed, for reclaiming this metal.

The preparation of two phase reaction product by make Mg complex compound/group 4 metal compounds low temperature (particularly higher than-10 ℃ but within the scope of lower than 50 ℃, preferably higher than-5 ℃ with lower than 40 ℃ between) under react to promote.To naturally trend towards being divided into the thicker phase of bottom and the lighter phase on upper strata due to two, need, preferably, under the existence of emulsion stabilizer, by stirring, reaction product is remained to emulsion.

In all embodiment of the present invention, emulsion (being two-phase liquid liquid system) can be by simple agitation and is optionally added (other) solvent and additive (the minimum agent (TMA) of all turbulent flows as described further below and/or emulsifying agent) to form.

Emulsifying agent/emulsion stabilizer can be used in addition with manner known in the art, for promoting the formation of emulsion and/or stablizing.For this object, can add, for example tensio-active agent, for example the class tensio-active agent based on acrylate copolymer or methacrylate polymer.Preferably, this emulsion stabilizer is acrylate copolymer or methacrylate polymer, particularly have middle-sized ester side chain (in ester side chain, have more than 10, preferably more than 12 carbon atoms and be preferably less than 30 and preferred 12 to 20 carbon atoms) emulsion stabilizer.Particularly preferred is unbranched C ₁₂to C ₂₀(methyl) esters of acrylic acid, such as poly-(methacrylic acid hexadecyl) ester and poly-(methacrylic acid octadecyl) ester.The suitable example of the available tensio-active agent of business is, for example, with (as 1-124 and 1-126) run after fame and weigh up the tensio-active agent of selling, as shown in before in the application.

As mentioned above, the minimum agent of turbulent flow (TMA) can be added reaction mixture to promote emulsion to form and to keep emulsion structure.This TMA reagent is necessary for inertia and soluble under reaction conditions in reaction mixture, and the meaning is that the polymkeric substance without the polar group polymkeric substance of straight or branched aliphatic carbon main chain (as have) is for preferred.

Particularly preferably, this TMA is selected from the alpha-olefinic polymer of the 'alpha '-olefin monomers with 6 to 20 carbon atoms, as poly-octene, poly-nonene, poly decene, poly-hendecene or poly-laurylene or its mixture.Poly decene most preferably.

TMA can be with the gross weight based on reaction mixture for example in 1ppm to 1.000ppm scope, preferably in 5ppm to 100ppm scope and more preferably the amount in 5ppm to 50ppm scope adds emulsion.

Have been found that ought be thicker oily group-4 metal/Mg mol ratio in 1 to 5 scope, preferably in 2 to 4 scopes, and group-4 metal/Mg mol ratio of external phase oil is in 55 to 65 scopes time, obtains best result.Conventionally, the ratio of the group-4 metal/Mg mol ratio in the group-4 metal/Mg mol ratio in external phase oil and thicker oil is at least 10.

By the disperse phase liquid that is heating and curing drop within the scope of 70 ℃ to 150 ℃, conventionally at 80 ℃ within the scope of 110 ℃, preferably carry out suitably at the temperature within the scope of 90 ℃ to 110 ℃.

For separated cured granulate, allow reaction mixture sedimentation and for example by siphon or stream inner filtration unit, cured granulate reclaimed from this reaction mixture.

Can by cured granulate product with hydrocarbon washing at least one times to as high as 6 times, preferably at least twice, most preferably at least three times, this hydrocarbon is preferably selected from aromatic hydrocarbon based and aliphatic hydrocarbon, be preferably toluene, heptane or pentane, more preferably toluene, particularly heat (for example at 80 ℃ within the scope of 100 ℃) toluene, may comprise in this hydrocarbon more in a small amount or the TiCl of a large amount more ₄.TiCl ₄amount can be at a few volume % to being greater than 50 volume %, such as 5 volume % to 50 volume %, preferably change in the scope of 5 volume % to 15 volume %.Also possibly, with the TiCl of 100 volume % ₄carry out at least once washing.

Washing optimizing can be had to catalyst component new and character needs to produce.

Finally, the catalyst component of washing is reclaimed.

Can, in addition for example by evaporation or catalyst component is dry with nitrogen wash, maybe can use or not use any drying step to make catalyst component be treated to oily liquids.

In addition, in the process of preparing, can add reductive agent at catalyst component, this reductive agent has reduced the amount of titanium that exist, that exist with oxidation state+4 in this cured granulate of olefin polymerization catalyst components.

Suitable aluminum compound has general formula A1R _3-nx _n, wherein R represents to have 1 to 20, preferably 1 to 10 and more preferably straight or branched alkyl group or the alkoxy base of 1 to 6 carbon atom, and X represents to be selected from the residue of the group of halogen (preferably chlorine) independently, and n represents 0,1 or 2.At least one residue in R residue is necessary for alkyl group.

Reclaim cured granulate in step (e2) before, can add this compound as optional compound catalyst component synthetic in and contact with the drop of the disperse phase of the emulsion stirring.That is, can be in step (b2) to step (d2) however arbitrary step in or in washing step process described above, in step (e2), before Al compound is added.With reference to WO2004/029112, EP-A-1862480 and EP _-a-1862481.

According to the present invention, alkylaluminium cpd to be used and the illustrative example of alkoxy aluminum compound are:

The add-on of optional Al compound depends on the reducing degree of the needs of the amount of titanium that exist, that exist with oxidation state+4 in the cured granulate of olefin polymerization catalyst components.The preferred amount of Al in catalyst component depends on Al compound to a certain extent, and for example, if use Al-alkoxy compound, the amount of preferred final AI seems such as fruit is used the amount of the final Al of alkyl chlorination Al compound for example low.

Alkylaluminium cpd or alkoxy aluminum compound and magnesium compound can be used alone or in combination.

Preferably, the alkylaluminium cpd or the alkyl alkoxy aluminum compound that limit are above added.

Preferably, step (e2) before, more preferably in washing step process, optional Al compound, Mg compound or its mixture are added, washing step comprise with identical or preferably different hydro carbons as washing medium at least one times, preferably twice and more preferably three washing process.

The alkylaluminium cpd using in catalyst component of the present invention can being prepared or alkoxy aluminum compound and/or magnesium compound add any washing medium, and as described above, washing medium is preferably toluene, heptane and/or pentane.

Although the procatalyst of the method according to this invention preparation can be carried out off and on, also preferably and likely, semicontinuous or Kaolinite Preparation of Catalyst component continuously.At this in semicontinuous or continuation method, by group II metal and the solution of the complex compound (by making the compound of this metal react to prepare in liquid organic reactant medium with this electron donor(ED)) of this electron donor(ED) and at least one compound of transition metal, at least one compound of transition metal may be dissolved in identical or different liquid organic reactant medium.Then, may be by the solution stirring obtaining like this under the existence of emulsion stabilizer, and then by the emulsion feed stirring like this to thermograde reactor, emulsion experience thermograde in thermograde reactor, the solidifying of drop that therefore causes the disperse phase of emulsion.Preferably, by the solution feed stirring to before thermograde reactor, optional TMA be included in the solution of complex compound or add solution.

When by the emulsion feed of this stirring during to thermograde reactor, the inert solvent that can drop be insoluble in wherein is in addition fed to gradient reactor, to promote drop to form and therefore cause the particle of the catalyst component of uniform particle size, when through this pipeline, this particle forms in thermograde reactor.This other solvent can be identical with liquid organic reactant medium, and it can be used for the solution of the complex compound of the above group II metal illustrating in greater detail of preparation.

Can the cured granulate of olefin polymerization catalyst components be reclaimed by stream inner filtration unit subsequently; then; optionally, for after removing some other washing steps and drying step of unreacted starting ingredient, the cured granulate of olefin polymerization catalyst components can be stored for using in addition.In one embodiment, can be by catalyst charge to olefin polymerization reactor, to guarantee continuous production and reactor feed after washing step.Also possibly, the catalyst component solidifying and wash is mixed with the fluid body of oiliness and catalyst component is stored and used as catalyst component-slurry oil material.Can avoid like this may be sometimes harmful to the form of catalyst component drying step.Oil-slurry methods is described in applicant's EP-A-1489110 substantially, and EP-A-1489110 is incorporated to the application by reference.

From the above description of semicontinuous or continuation method, can find out, therefore possible that: different process step is used to independently reaction vessel; With the reaction product of preparing in each reaction vessel of transfer; With reaction product in-line is fed to other reaction vessel, for the formation of emulsion and cured granulate subsequently.

Preferably, use full continuation method, because the time of saving in the method is significant.In this full continuation method, the formation of cured granulate can be carried out in the thermograde pipeline in tubular reactor, and this thermograde pipeline sufficiently long and experience is this thermograde to as high as " solidifying " temperature within the scope of 70 ℃ to 150 ℃ from the starting temperature in 20 ℃ to 80 ℃ lower scopes.Preferably, by applying common well heater, microwave etc., from indirect heating tubular reactor, obtain this thermograde.

As previously mentioned, preferably can use filtering unit, for cured granulate is filtered from solvent streams.About this filtering unit, can use various reels and screening system, depend on specific granularity.

With two kinds of preparation methods, what the final ingredient of solid catalyst obtaining needed is that form is particle, this particle has conventionally within the scope of 2 μ m to 500 μ m, preferably within the scope of 5 μ m to 200 μ m and more preferably passing through within the scope of 10 μ m to 100 μ m used Coulter counter LS200 in the lower size ranges of measuring as medium with normal heptane of room temperature (20 ℃), and even the size ranges within the scope of 20 μ m to 60 μ m is possible.

Measure by Ku Er special formula method and size-grade distribution that be defined as SPAN, catalyzer of the present invention depends on preparation method.Use the size-grade distribution of emulsification/curing conventionally low than using the size-grade distribution of intermediate processing.Yet, needing, the size-grade distribution of the ingredient of solid catalyst of preparing according to intermediate processing is low as far as possible, and even more preferably similar to the size-grade distribution of the ingredient of solid catalyst of preparing according to emulsification/curing.

Preferably, size-grade distribution 0.5 to maximum 4.0 scopes, more preferably 0.5 to maximum 3.0 scopes and even more preferably 0.5 to maximum 2.0 scopes.

SPAN is defined as

\frac{d 90 [μm] - d 10 [μm]}{d 50 [μm]}

Wherein d90 represents the particle diameter under 90% accumulated size, and d10 represents the particle diameter under 10% accumulated size, and d50 represents the particle diameter under 50% accumulated size.

Prepared according to the methods of the invention catalyzer has form and granularity and the size-grade distribution needing and is applicable to the polymkeric substance that preparation has the polymer property needing.

The present inventor finds unexpectedly, having the form that needs and the catalyst component particle of granularity and size-grade distribution can obtain by precipitating or prepare emulsification/curing mode of Z-N (ZN) type catalyzer by common mechanism, and is applicable to alkene (as ethene or propylene, particularly propylene) and the optional C that is selected from ₂to C ₁₂monomer (preferred C ₂to C ₆the polymerization of other comonomers monomer).

Therefore, another object of the present invention is to provide the catalyst component that a kind of form is solid particulate (for example, by method described above) and its purposes for the preparation of catalyst system applicable in olefine polymerizing process.

Catalyst according to the invention component has good form, good size-grade distribution, and produces the polymerizing catalyst with most suitable polymerization activity.According to print effect, polymer beads prepared by the catalyst component of the application of the invention also has good morphological feature.

It is important that not only catalyzer form, and catalyzer forms in the character of needs that obtains polymkeric substance.As shown in before the application, the character of such needs is good hydrogen response and low degree of randomness.

As mentioned above, the application's catalyzer has: within the scope of 1.0 % by weight to 10.0 % by weight, preferred within the scope of 1.5 % by weight to 8.5 % by weight and more preferably group-4 metal (the being preferably Ti) content within the scope of 2.0 % by weight to 7.0 % by weight; Within the scope of 5.0 % by weight to 22.0 % by weight, preferred within the scope of 6.0 % by weight to 20.0 % by weight and more preferably group II metal (the being preferably Mg) content within the scope of 6.5 % by weight to 18.0 % by weight; Within the scope of 0.0 to 0.8 % by weight, preferably at 0.0 to 0.5 % by weight and the more preferably Al content within the scope of 0.0 to 0.4 % by weight.

The amount of Ti, Mg and Al is measured by the icp analysis of describing at experimental section.

The inner amount of body of giving, within the scope of 1.0 % by weight to 50.0 % by weight, preferably within the scope of 1.3 % by weight to 40.0 % by weight and more preferably within the scope of 1.5 % by weight to 35.0 % by weight, and is measured by HPLC or GC conventionally.

Maximum can the calculating according to following formula to the scale of construction that may exist in ingredient of solid catalyst:

100-(3.917*Mg%+4.941*Al%+3.962*Ti%)=maximum give the scale of construction (%)

It is to be MgCl based on all Mg ₂form, all Al be AlCl ₃form and all Ti be TiCl ₄form and there is not the hypothesis of hydro carbons.

Catalyst component preparation of the present invention, based on liquid/liquid two-phase system (emulsification/curing) or intermediate processing, wherein in both cases, does not need independent outer carrier material (such as silicon-dioxide or MgCl ₂) to obtain solid catalyst particle.

The polymerization process that catalyst component of the present invention can be used for wherein comprises at least one polymerization stage, in this polymerization stage polymerization, typically with solution phase, slurry phase, body phase or gas phase, carries out.Typically, polymerization process comprises other polymerization stage or polymerization reactor.In a specific embodiment, the method comprises at least one bulk reaction device region and at least one Gas-phase reactor region, and each region comprises at least one reactor and all reactor cascade layouts.In a particularly preferred embodiment, the polymerization process for polymerizable alkenyl hydro carbons (particularly propylene and optional as the comonomer of ethene or other alpha-olefines) comprises at least one bulk reaction device and at least one Gas-phase reactor being disposed in order with this.In some preferred method, the method comprises a bulk reaction device and at least two (for example two or three) Gas-phase reactor.The method can comprise front reactor and post-reactor in addition.Front reactor typically comprises pre-polymerization reactor.In these class methods, preferably in the some or all of reactors of cascade reactor, use higher polymerization temperature (70 ℃ or higher, preferably 80 ℃ or higher, even 85 ℃ or higher), so that polymkeric substance reaches some special properties.

In order to prepare according to homopolymer polypropylene of the present invention or polypropylene copolymer, the catalyst system of use also comprises organic metal promoters except catalyst component described above, that form is solid particulate.

Therefore, preferably, from the group being formed by following compound, select promotor: trialkylaluminium, as triethyl aluminum (TEA), triisobutyl aluminium, three n-butylaluminum; Dialkylaluminum chloride, as dimethylaluminum chloride or diethyl aluminum chloride; With alkyl sesquialter aluminum chloride.More preferably, promotor is triethyl aluminum or diethyl aluminum chloride, most preferably, triethyl aluminum is used as to promotor.

Optionally, use one or more external donors, should can typically be selected to body, for example silane or any other external donors well known in the art.External donor is known and in propylene polymerization, is used as stereospecific conditioning agent in this area.External donor is preferably selected from-oxyl silane compound, amino silane compounds and-oxyl alkane compound.

Typical-oxyl silane compound has formula (II)

R ⁷ _pSi(OR ⁸) _4-p (II)

Wherein

R ⁷for α-side chain C ₃to C ₁₂alkyl or β-side chain C ₃to C ₁₂alkyl,

R ⁸for C ₁to C ₁₂alkyl, and

P is the integer in 1 to 3 scope.

As external electrical, to the more specifically example of the-oxyl silane compound of body, be in the present invention: dimethoxydiphenylsilane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, cyclopentyl-methyl dimethoxy silane, cyclopentyl-methyl diethoxy silane, Dicyclohexyldimethoxysilane, dicyclohexyl diethoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl methyl diethoxy silane, aminomethyl phenyl dimethoxy silane, phenylbenzene diethoxy silane, cyclopentyl-trimethoxy-silane, phenyltrimethoxysila,e, cyclopentyl triethoxyl silane, phenyl triethoxysilane.

Most preferably, the alkoxysilane compound containing trialkylsilyl group in molecular structure that has a formula (II) is dicyclopentyl dimethoxyl silane or Cyclohexyl Methyl Dimethoxysilane.

Typical amino silane compounds has formula (III)

Si(OR ⁹) ₃(NR ¹⁰R ¹¹)

Wherein

R ⁹for thering is the hydrocarbyl group of 1 to 6 carbon atom, R ¹⁰for thering is the hydrocarbyl group of 1 to 12 carbon atom or hydrogen atom, and R ¹¹for thering is the hydrocarbyl group of 1 to 12 carbon atom.

Preferably, these compounds have formula (IV)

Si(OCH ₂CH ₃) ₃(NR ¹⁰R ¹¹)

Wherein

R ¹⁰with R ¹¹independently selected from the group being formed by following group: have 1 to 12 carbon atom straight chain aliphatic hydrocarbon group, there is the side chain aliphatic hydrocarbon group of 1 to 12 carbon atom and there is the ring-shaped fat hydrocarbyl group of 1 to 12 carbon atom.

Particularly preferably be R ¹⁰with R ¹¹independently selected from the group being formed by following group: methyl, ethyl, n-propyl, normal-butyl, octyl group, decyl, sec.-propyl, isobutyl-, isopentyl, the tertiary butyl, tert-pentyl, neo-pentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and suberyl.More preferably, R ¹⁰with R ¹¹identical and there is 1 to 6 carbon atom, more more preferably, R ¹⁰with R ¹¹for C ₁to C ₄alkyl group.

Most preferably, the external donor being represented by formula (III) or formula (IV) is diethylin triethoxyl silane.

Therefore, the external donor for catalyst system is preferably diethylin triethoxyl silane, dicyclopentyl dimethoxyl silane or Cyclohexyl Methyl Dimethoxysilane.

Embodiment

Experimental section

1, method

Melt flow rate (MFR) MFR:ISO1133; 230 ℃, 2.16kg load.

Size-grade distribution PSD:

Coulter counter LS200, at room temperature, uses heptane as medium.

Mean particle size is usingd μ m and is provided and at room temperature use normal heptane to measure with Coulter counter LS200 as medium; Granularity determination of transmission electron microscopy lower than 100 μ m.

Median particle (d50) is usingd μ m and is provided and at room temperature use normal heptane to measure with Coulter counter LS200 as medium.

Granularity (d10) is usingd μ m and is provided and at room temperature use normal heptane to measure with Coulter counter LS200 as medium.

Granularity (d90) is usingd μ m and is provided and at room temperature use normal heptane to measure with Coulter counter LS200 as medium.

SPAN limits as follows:

\frac{d 90 [μm] - d 10 [μm]}{d 50 [μm]}

Icp analysis (Al, Mg, Ti)

The solid sample that the ultimate analysis of catalyzer is M by the quality used in dry cooled on ice carries out.By at nitric acid (HNO ₃, 65%, V 5%) and fresh deionization (DI) water (V 5%) in dissolve diluted sample to known volume V.By solution in addition with DI water dilution until final volume V and stablizing two hours.

Analyze at room temperature and carry out with the hot element iCAP6300 inductively coupled plasma-emission spectrometer of use (ICP-OES), ICP-OES is used Al, Mg and the standard of Ti in 5%HNO3 solution of blank (solution of 5% nitric acid) and 0.5ppm, 1ppm, 10ppm, 50ppm, 100ppm and 300ppm to calibrate.

Before analysis starts, use immediately blank and 100ppm standard to make calibration " replacement slope (reslope) ", (Al of 20ppm, Mg and Ti are containing 5%HNO to the quality control of running sample ₃, 3%HF DI water in solution in) to confirm this replacement slope.After every 5 samples and when predetermined analysis bank finishes, also move QC sample.

The content of Mg is used the content of the monitoring of 285.213nm line and Ti to use the monitoring of 336.121nm line.Al concentration in ICP sample is between 0ppm to 10ppm (only calibrating to 100ppm) time, and the content of aluminium is monitored by 167.079nm line, and to the Al concentration higher than 10ppm, by 396.152nm line, monitors.

The value recording is for three continuous aliquot mean values from same sample and pass through the original quality of sample relevant to original catalyst with dilution volume Input Software.

In catalyst component, give the mensuration of the amount of body

The mensuration of the amount of giving body in catalyst component is used HPLC (UV-detector, RP-8 post, 250mm * 4mm) to carry out.Use pure donor compound preparation standard solution.50-100mg catalyst component is weighed and enters (weighing precision is 0.1mg) in 20ml bottle.10ml acetonitrile is added and by sample suspension supersound process 5-10min in ultra sonic bath.Acetonitrile suspension is suitably diluted and use 0.45 μ m strainer liquid sample to be filtered to the sample bottle of HPLC instrument.From HPLC, obtain peak height.

Use following equation to calculate in catalyst component the percentage composition of body:

Percentage composition (%)=A ₁cVA ₂ ^-1m ^-10.1%

Wherein

A ₁=sample peak height

The concentration of c=standardized solution (mg/l)

The volume of V=sample solution (ml)

A ₂=standard peak height

The weight of m=sample (mg)

By analyzing to body of GC

The solid sample that is M by functional quality to body analysis of catalyzer carries out, and the methylene chloride of about 2ml is added.Then about 1ml deionized water is added to bottle.Finally, the interior mark nonane that is N by known quality adds.Then by mixture supersound process 15min, dissolve completely guaranteeing.After supersound process, by sample sedimentation, be two phases and the aliquot of organic phase is removed, then used 0.45 μ m nylon filter to be filtered in the bottle that is applicable to gas chromatograph.

Analyze with the Perkin Elmer Auto System XL gas chromatograph that comprises splitting ring syringe and flame ionization detector and carry out.Post is DB-1, and length is 30m, has the internal diameter of 0.32mm and the phase thickness of 0.25 μ m.System is tilted to be warming up to before 250 ℃ with 10 ℃/min, system is stopped 5 minutes at 40 ℃, by system remain on 250 ℃ other 4 minutes.If need, top temperature be increased to 300 ℃.

Calculation result in the following manner:

Wherein:

Ax=component area

F=component coefficient

The quality of mark (nonane) in N=, mg

The area of mark (nonane) in Ay=

The coefficient of mark (nonane) in Fistd=

The quality of M=sample, mg

The xylene soluble fraction of product at xylene soluble part XS:25 ℃.

Under agitation by 2.0g polymer dissolution in the 250ml p-Xylol of 135 ℃.After 30 ± 2 minutes, allow at ambient temperature solution cooling 15 minutes, and then at 25 ± 0.5 ℃, allow solution sedimentation 30 minutes.Solution is filtered with filter paper in two 100ml flasks.Solution from first 100ml container is evaporated in nitrogen gas stream and residue is dried until reach constant weight under vacuum at 90 ℃.

XS％＝(100xm1xv0)/(m0xv1)

The amount of m0=initial polymer (g)

The weight of m1=residue (g)

V0=original volume (ml)

The volume of the sample that v1=is analyzed (ml)

Degree of randomness

With Nicolet Magna IR Spectrometer550, carry out infrared (IR) spectroscopic analysis.At 230 ℃, by polymer powder, prepare 220-250 μ m film, subsequently it is cooled to rapidly to room temperature.All IR analyze and complete in two hours of film preparation.Use is normalized to the peak height of internal reference band (by above ¹³the calibration of C NMR result) peak area obtains quantitative co-monomer content.Ethene is used 733cm ^-1(baseline 690-780cm ^-1) band, the 809cm that locate ^-1(baseline 750-890cm ^-1) reference tape located is quantitative.The amount (degree of randomness) of separated ethylene unit is used 733cm ^-1(baseline 690-780cm ^-1) peak height of the band of locating and the reference tape identical with reference tape described above estimates.Calibration is by obtaining above ¹³c NMR result is carried out.

Degree of randomness=random ethylene (P-E-P-) content/total ethylene content * 100%

Respond in example described above is carried out under inert conditions.

Example

Example 1:

The preparation of soluble alkoxyl magnesium

By preparing below alkoxyl magnesium solution: in 80 minutes in 300ml glass reactor, by BOMAG 220.0ml, 20% (Mg (butyl) _1,5(octyl group) _0,5from Crompton GmbH) solution in toluene under agitation adds the 2-Ethylhexyl Alcohol (from Merck Chemicals) of 50.0ml and the mixture of 25.0ml butoxy propyl alcohol (from Sigma-Aldrich) (mol ratio 2-Ethylhexyl Alcohol/butoxy propyl alcohol=1.9, and mol ratio alcohol/Mg=2.2).In adition process, the mixture in reactor is remained lower than 25 ℃.After having added of BOMAG, the mixing of the reaction mixture at 25 ℃ is continued other 60 minutes.Then the temperature of reaction mixture is elevated to 60 ℃ and at this temperature, continue to stir 60 minutes in 14 minutes, has at this moment reacted.

Example 2: intermediate processing

In 300ml glass reactor, by the TiCl of 20ml ₄be heated to 90 ℃ with the heptane of x ml.Mixing velocity is set to 150rpm.Then will to the mixture of the Viscoplex of body and x ml, slowly add according to 30ml alkoxyl magnesium, the x ml of example 1 preparation.After 30 minutes, mixing is stopped and allowing granules of catalyst sedimentation.After sedimentation, the level by liquid siphon to about 20ml.

Then the 100ml toluene wash 0.5h with 90 ℃ by granules of catalyst, next uses twice of heptane wash (each: 100ml, 30min) and finally with pentane, washs once (100ml, 30min).In heptane wash process for the second time, temperature is reduced to room temperature.

Details can be as seen from Table 1.

Example 3: the preparation of ingredient of solid catalyst (emulsification approach):

By the TiCl of 19.5ml ₄add 300ml glass reactor.Mixing velocity is set to 170rpm.Then 30ml alkoxyl magnesium, the x ml of preparation as described above are slowly added to the mixture of body, temperature is remained lower than 25 ℃.After five minutes, the 1ml toluene solution of the Viscoplex by x ml and Necadd is mixed to the solution forming and add.Then x ml heptane is added, and after 5 minutes, in 17min, mixing temperature is elevated to 90 ℃.After 30 minutes, mixing is stopped and allowing granules of catalyst sedimentation.After sedimentation, liquid siphon is walked.

Then the 100ml toluene wash 0.5h with 90 ℃ by granules of catalyst, next uses heptane (100ml, 30min) and pentane (100ml, 20min) washing.In heptane wash process, temperature is reduced to room temperature.

Details can be as seen from Table 1.

Use following inner to body:

2,2-bis-(2-tetrahydrochysene furan is fed base) propane (giving body A)

Two (methoxymethyl)-2 of 3,3-, 6-dimethyl heptane (giving body B)

Two (the ethoxyl methyl)-2-methyl dodecanes of 3,3-(giving body C)

Two (ethoxyl methyl)-2 of 3,3-, 6-dimethyl heptane (giving body D)

4-oxyethyl group-3-(ethoxyl methyl) heptane (giving body E)

2,2-diisobutyl-1,3-Propanal dimethyl acetal (giving body F)

Two (methoxymethyl) fluorenes of 9,9-(giving body G)

Two (butoxymethyl)-2 of 3,3-, 6-dimethyl heptane (giving body H)

4-methoxyl group-3-(methoxy methyl base heptane (giving body I)

4-butoxy-3-(butoxymethyl) heptane (giving body J)

Two (methoxymethyl) heptane of 3,3-(giving body K)

Two (ethoxyl methyl) heptane of 3,3-(giving body L)

Two (2-ethyl hexyl oxy) naphthalenes of 1,8-(giving body M)

Comparative example 1:CE1

As a comparison case, by according to the emulsification/curing of the example 5 of EP1403292, use dichloride phthalyl as internal activator presoma (according to the example 1 preparation Mg complex compound of EP1403292) (Mg13.2 % by weight, Al0.4 % by weight, the phthalic acid two (2-ethylhexyl) of Ti3.5 % by weight and 29.9 % by weight is as the inner body of giving; Amount use HPLC measurement to body) carry out Kaolinite Preparation of Catalyst.

Table 1

Preparation type: e is used for according to the emulsification described in example 3

P is used for according to the precipitation described in example 2

* will first be dissolved in a small amount of toluene to body G

¹) amount to body of using GC to measure

Nm....... unmeasured

Example 4

Use 5 liters of stainless steel reactors for propylene polymerization.

Using the 0.9ml triethyl aluminum (TEA) as promotor (from Witco, directly use), as about 0.13ml dicyclopentyl dimethoxyl silane (DCDS) (from Wacker, with molecular sieve drying) and the mixing of 30ml Skellysolve A of external donor and allow it to react 5 minutes.Then a semifused is added to polymerization reactor and second half and about 20mg catalyst mix.After in addition 5 minutes, catalyzer/TEA/ is added to reactor to body/Skellysolve A mixture.Al/Ti ratio is that 250 moles/mole and Al/DCDS ratio are 10 moles/mole.200 mmole hydrogen and 1400g propylene are introduced to reactor and temperature are elevated to polymerization temperature (80 ℃) in about 15 minutes.Reaching polymerization temperature polymerization time is afterwards 60 minutes, afterwards the polymkeric substance of formation is taken out from reactor.

Table 2: polymerization result

P is used for according to the precipitation described in example 2

Nm....... unmeasured

As can be seen from Table 2, catalyst according to the invention has produced the product with higher MFR, follows with the comparative catalyst with the combination of low XS value and compares, and this product demonstrates better hydrogen response.

Example 5: copolymerization

Use 5 liters of stainless steel reactors for propylene polymerization.

Using the 264 μ l triethyl aluminums (TEA) as promotor (from Witco, directly use), as 45 μ l dicyclopentyl dimethoxyl silanes (DCDS) (from Wacker, with molecular sieve drying) and the mixing of 30ml Skellysolve A of external donor and allow it to react 5 minutes.Then a semifused is added to polymerization reactor and second half and 30mg catalyst mix.Catalyzer in this example is identical with the catalyzer using in example 3 and have a titanium of 3.3 % by weight.After in addition 10 minutes, catalyzer/TEA/ is added to reactor to body/Skellysolve A mixture.Al/Ti ratio is that 250 moles/mole and Al/DCDS ratio are 10 moles/mole.130 mmole hydrogen and 1400g propylene are introduced to reactor and temperature are elevated to polymerization temperature (70 ℃) in about 15 minutes.Start to raise temperature (at approximately 40 ℃) 5 minutes afterwards, starts ethylene feed, and in polymerization process by the ethene continuously feeding of 26.6g altogether.Reaching polymerization temperature polymerization time is afterwards 60 minutes, afterwards the polymkeric substance of formation is taken out from reactor.Output is 509g.

Comparative example 2:CE2 copolymerization

According to example 5, carry out this example, except following: catalyzer is identical with the catalyzer of describing in CE1 and have a titanium of 3.1 % by weight, the amount of catalyzer is 11.1mg, and the amount of TEAL is that 300 μ l (Al/Ti mol ratio is 305) and Al/Do (Al/ is to body) mol ratio are 10.Output is 549g.

Comparative example 3:CE3 copolymerization

According to comparative example, CE2 carry out this example, catalyzer is identical with the catalyzer of describing in CE1 and have the titanium of 3.1 % by weight, except following: the amount of TEAL be 300 μ l (Al/Ti mol ratio is 242) and Al/Do mol ratio be 10 and the amount of the ethene of charging be 26.4g.Output is 502g.

Comparative example 4:CE4 copolymerization

According to comparative example, CE2 carry out this example, except following: catalyzer is identical with the catalyzer of describing in CE1 and have the titanium of 3.1 % by weight, and the amount of TEAL is 300 μ l (Al/Ti is 202 moles/mole), and Al/Do is 10.Output is 414g.

The result of copolymerization example can be found out in table 3:

Table 3: copolymerization result

Polymerization	Unit	Example 5	CE2	CE3	CE4
						Catalyzer		*	CE1	CE1	CE1
Ti in catalyzer	[% by weight]	3.3	3.1	3.1	3.7
						The amount of catalyzer	[mg]	11.2	11.1	14	14.1
C ₂-charging	[g]	26.6	26.6	26.4	26.6
						Output	[g]	509	549	502	414
Active	[kgPP/gcath]	45.4	58.5	35.9	29.4
						MFR ₂	[g/10min]	9.3	4	5.1	4.8
C in polymkeric substance ₂	[% by weight]	4.2	3.5	4	4.7
						Degree of randomness	[％]	71.3	78.5	75.1	72.2
XS	[% by weight]	9	4.9	7.5	11

* use to body D and according to the catalyzer of example 3 preparations

From table 3 and Fig. 1, can find out, at identical C ₂under content, have diether as inside to degree of randomness body, that catalyst according to the invention produces than have phthalic ester as inside the degree of randomness low at least 3% to catalyzer body, comparative example.

Claims

1. an ingredient of solid catalyst, has

B) within the scope of 5.0 % by weight to 22.0 % by weight, preferably within the scope of 6.0 % by weight to 20.0 % by weight, the more preferably group II metal within the scope of 6.5 % by weight to 18.0 % by weight, preferred Mg content (measuring by icp analysis);

D) within the scope of 2 μ m to 500 μ m, preferably within the scope of 5 μ m to 200 μ m, the more preferably mean particle size within the scope of 10 μ m to 100 μ m (by using Coulter counter LS200 to measure at 25 ℃ in normal heptane);

Wherein in formula (I) and formula (II)

R in formula (I) ₃and R ₄identical or different, and can be H or straight or branched C ₁to C ₁₂alkyl, or R ₃and R ₄can form together the ring with 5 to 10 C atoms, described ring can be has the aliphatics of 9 to 20 C atoms or a part for aromatic series polycyclic system,

2. a method for the olefin polymerization catalyst components that is solid particulate for the preparation of form according to claim 1, comprises the following steps:

A) prepare the solution of at least one alkoxy compound (Ax), at least one compound that described alkoxy compound (Ax) is group II metal and the reaction product of at least one monohydroxy-alcohol (A) in liquid organic reactant medium,

B) described solution is added at least one compound of transition metal, and

C) prepare ingredient of solid catalyst particle,

Wherein in formula (I) and formula (II):

3. method according to claim 2, the reaction product of the mixture of the reaction product of at least one compound that wherein said alkoxy compound (Ax) is group II metal and monohydroxy-alcohol (A) or at least one compound of group II metal and monohydroxy-alcohol (A) and other alcohol (B), described alcohol (B) also comprises except hydroxylic moiety different from described hydroxylic moiety, at least one other oxy radical.

4. method according to claim 2, wherein except described at least one alkoxy compound (Ax), the reaction product of at least one compound that at least one alkoxy compound (Bx) is group II metal and alcohol (B), described alcohol (B) also comprises except hydroxylic moiety different from described hydroxylic moiety, at least one other oxy radical.

5. according to the method in claim 2 or 3, wherein said monohydroxy-alcohol (A) is for having the monohydroxy-alcohol of formula ROH, and wherein R is straight or branched C ₁to C ₂₀alkyl.

6. according to the method described in claim 3 or 4, wherein, in described alcohol (B), described other oxy radical is ether moiety.

7. according to the method described in claim 3,4 or 6, wherein said alcohol (B) is C ₂to C ₄glycol monoether, wherein said ether moiety comprises 2 to 18 carbon atoms.

8. according to method in any one of the preceding claims wherein, wherein said group II metal is magnesium.

9. according to method in any one of the preceding claims wherein, wherein said transition metal is group-4 metal and/or the 5th family's metal, is preferably Ti.

10. according to method in any one of the preceding claims wherein, the preparation of the described olefin polymerization catalyst components that wherein form is solid particulate comprises the following steps:

(a1) prepare the solution (S1) of at least one alkoxy compound (Ax), the reaction product of the electron donor(ED) of at least one compound that described at least one alkoxy compound (Ax) is group II metal and at least one monohydroxy-alcohol (A) and formula (I) or formula (II) in liquid organic reactant medium (OM1)

(b1) by described solution (S1) and at least one transistion metal compound (CT) combination, and

(c1) the described catalyst component that precipitation forms is solid particulate, and

(d1) reclaim the cured granulate of described olefin polymerization catalyst components.

11. methods according to claim 10, wherein in step (b1), described solution (S1) is added at the temperature of described at least one transistion metal compound (CT) within the scope of 50 ℃ to 110 ℃ and carry out, at described temperature, described at least one transistion metal compound (CT) is liquid form, the precipitation that causes described ingredient of solid catalyst, thus in described step (a1) or described step (b1), can add tensio-active agent.

12. methods according to claim 10, wherein described at least one transistion metal compound (CT) of described solution (S1) and liquid form is mixed at the temperature within the scope of approximately-20 ℃ to approximately 30 ℃, and precipitate described ingredient of solid catalyst by subsequently temperature being slowly elevated in the temperature range of 50 ℃ to 110 ℃, thereby the speed that temperature raises within the scope of 0.1 ℃ of per minute to 30 ℃ per minute, be preferably within the scope of 0.5 ℃ of per minute to 10 ℃ per minute, thereby and before tensio-active agent is added to described solution (S1) in described step (b1).

13. according to the method described in any one in claim 2 to 9, and the described preparation of the described catalyst component that wherein form is solid particulate comprises the following steps:

(a2) prepare the solution of at least one alkoxy compound (Ax), the reaction product of the electron donor(ED) of at least one compound that described at least one alkoxy compound (Ax) is group II metal and at least one monohydroxy-alcohol (A) and formula (I) or formula (II) in liquid organic reactant medium

(b2) the described solution of described alkoxy compound (Ax) is added at least one compound of transition metal with preparation emulsion, the disperse phase of wherein said emulsion is drop form and comprises the described group II metal in the described alkoxy compound (Ax) that is greater than 50 % by mole

(c2) stir described emulsion, the described drop of described disperse phase is remained in the predetermined size ranges of 2 μ m to 500 μ m,

(d2) solidify the described drop of described disperse phase,

(e2) reclaim the described cured granulate of described olefin polymerization catalyst components.

14. methods according to claim 13, is characterized in that, described method is carried out continuously.

The particle of 15. 1 kinds of catalyst components, the particle of described catalyst component can obtain according to any one in claim 2 to 14.

16. 1 kinds of olefin polymerization catalysis, comprise according to the particle of the catalyst component described in claim 1 or 15 and be preferably the promotor of aluminum alkyl catalyst and optional external electrical to body.

17. as the purposes of the catalyzer limiting in claim 16 for olefin polymerization and optional comonomer, and described alkene is C particularly ₂to C ₁₀alpha-olefin, be preferably ethene or propylene, described comonomer is selected from C ₂to C ₁₂monomer.